CN103827056B - The base material be made up of the ceramic matrix composites comprising SiC is formed the method for level and smooth enamel coating, and the parts be made up of the ceramic matrix composites being provided with described coating - Google Patents

The base material be made up of the ceramic matrix composites comprising SiC is formed the method for level and smooth enamel coating, and the parts be made up of the ceramic matrix composites being provided with described coating Download PDF

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Publication number
CN103827056B
CN103827056B CN201280043276.7A CN201280043276A CN103827056B CN 103827056 B CN103827056 B CN 103827056B CN 201280043276 A CN201280043276 A CN 201280043276A CN 103827056 B CN103827056 B CN 103827056B
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China
Prior art keywords
coating
glass
enamel
base material
silicon
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CN103827056A (en
Inventor
P·迪斯
L·蒙塔涅
S·佩雷-维拉尔
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Centre National de la Recherche Scientifique CNRS
Safran Ceramics SA
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Centre National de la Recherche Scientifique CNRS
Herakles SA
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2205/00—Compositions applicable for the manufacture of vitreous enamels or glazes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Glass Compositions (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)

Abstract

The present invention relates to a kind of method, comprising: at the whole deposited on silicon refractory cements thickener of base material, described thickener primarily of silicon-dioxide and aluminum oxide composition and and liquid mixing, the hollow space of the celature on described surface filled by described cement thickener; Heat-treat after theing cement solidifies thus solidify described cement, thus obtaining the first layer (22) of refractory cements coating; Deposited furnish on the first layer, described slurry is made up of the glass powder floated on a liquid and primarily of the powder constituent of silicon-dioxide, boron oxide, aluminum oxide and at least one alkalimetal oxide; Carry out the thermal treatment for being coated with by softening and sprawling described glass thus obtain the second coating (24), described second coating (24) formed covers the enamel of described the first layer, select the composition of described glass powder thus formed coating temperature lower than 1100 DEG C and second-order transition temperature lower than the glass of 750 DEG C.

Description

The base material be made up of the ceramic matrix composites comprising SiC is formed the method for level and smooth enamel coating, and the parts be made up of the ceramic matrix composites being provided with described coating
Technical field
The present invention relates to the coating being formed on the base material of ceramic substrate complex body (CMC) material comprising silicon carbide (SiC) and there is the smooth outer surface of enamel outward appearance.
The present invention is specially adapted to the parts be used in turbine engine, is particularly applicable to the parts standing high temperature in use, such as: the rear body member of engine blade or fin or aero-turbine.
Background technology
Research for higher efficiency and lower disposal of pollutants has caused for the continuous service temperature raised of turbine engine imagination.Therefore built view uses CMC material to replace metal alloy thus makes the heating part of turbine engine.The remarkable part of CMC material is its mechanical properties (described mechanical properties makes it be applicable to forming structure unit) and at high temperature keeps the ability of these character.In addition, compared to metal alloy, CMC material has lower density and therefore realizes the saving of weight.
CMC material is made up of fibre-reinforced part, and described fibre-reinforced part is made up of the refractory fibre (carbon fiber or ceramic fiber) by ceramic substrate densification.CMC material involved is herein have those of the ceramic substrate that comprises SiC, particularly ceramic substrate make primarily of SiC those.The representative instance of these CMC material is C-SiC material (reinforcement be made up of carbon fiber and the matrix be made up of SiC), SiC-SiC material, with matrix mixing or the material that is arranged in order, such as, there is the material of the C/SiC matrix of mixing or have by SiC phase and RESEARCH OF PYROCARBON (PyC) phase or norbide (B 4c) mutually or the ternary Si-B-C system material of matrix that alternates and make.
But CMC material has the appearance of corrugated and relative coarseness, and can find that the aerodynamic performance needed for described appearance and turbine engine components is incompatible.Ripple in surface is the fibre-reinforced part owing to usually weaving, and anchor is relevant with the mode of acquisition matrix, and matrix is formed by chemical vapor infiltration (CVI) usually.
Therefore proposed as this CMC parts arrange smooth finish thus the level and smooth appearance of member of imparting.Document WO2010/112768 describes and forms this smooth finish with the form of glass, and described glass is substantially by silicon-dioxide (SiO 2), aluminum oxide (Al 2o 3), barite (BaO) and lime (CaO) composition, there is the melt temperature being more than or equal to 1300 DEG C.
The material comprising SiC is formed the glassy coating of protectiveness be described in other documents.
Therefore, paper " Glass coating for SiCf/SiC composites for high-temperature application " (the Acta Mater of the people such as M.Ferraris, 48 (2000), 4721-4724 page) describe to be formed on SiC/SiC complex body base material and be essentially the borosilicate type (SiO of 70.4 % by weight 2, 2.1 % by weight Al 2o 3, 17.5 % by weight B 2o 3, 10 % by weight BaO) glass coating.In order to avoid there is bubble in glassy coating, melten glass temperature of glazing on base material is increased to about 1300 DEG C, and the viscosity of glass is enough low thus be convenient to degassed at such a temperature.
The paper " Oxidation protective glass coating for SiC coated carbon/carbon composites for application at1773K " (Mat.Lett.60 (2006), 431-434 page) of the people such as F.Qian-Gang have studied by the borosilicate type (SiO of 72 % by weight-82 % by weight substantially 2, 2 % by weight-5 % by weight Al 2o 3, 8 % by weight-15 % by weight B 2o 3, 1 % by weight-3 % by weight Li 2o, 2 % by weight-5 % by weight Y 2o 3) the anti-oxidation protection coating made of glass.Scanning electron microscope image shows the coatingsurface with hole.
The paper " Effect of glass sealing on the oxidation behavior of three-dimensional C/SiC composites in air " (Carbon39 (2001), 1127-1133 page) of the people such as Cheng describes and uses the borosilicate glass (SiO of 55 % by mole-60 % by mole 2with the B of 40 % by mole-45 % by mole 2o 3) thus form selfreparing protective coating on C-SiC complex body.Selfreparing temperature in the scope of 700 DEG C to 900 DEG C, i.e. the softening temperature can filling the crack existed in coating of glass.
Need a kind of method, described method makes likely in the CMC material comprising SiC, to form coating, and described coating has smoothly and is advantageously the surface of enamel outward appearance, the not defect of such as bubble or hole.Except above-mentioned thermodynamic property, the advantage that this coating has is the damage being derived from impact being easy to detection or even minimum.
Summary of the invention
The present invention is devoted to provide this method, and for this purpose, proposes a kind ofly on the base material of ceramic matrix composites, to form the method with the coating of the smooth outer surface of enamel outward appearance, and described method comprises:
At the deposited on silicon refractory cements thickener of described base material, described thickener is by being formed with the powder of liquid mixing primarily of silicon-dioxide and aluminum oxide composition, and described cement thickener fills the hollow space in the fluctuating on described surface thus reduce its irregularity and cover the whole surface of described base material;
Heat-treat after theing cement solidifies thus solidify described cement, thus obtaining the first coating of refractory cements;
Deposited furnish (barbotine) in described first coating, described slurry is formed by the glass powder in liquid suspension, and described glass powder is formed primarily of the powder of silicon-dioxide, boron oxide, aluminum oxide and at least one alkalimetal oxide; With
Carry out the thermal treatment for glazing by softening and sprawling described glass thus obtain the second coating, described second coating formation covers the enamel of described first coating;
Select the composition of described glass powder thus formed glazing temperature lower than 1100 DEG C and second-order transition temperature lower than the glass of 750 DEG C.
The remarkable part of described method is following aspect:
The first layer of refractory cements is formed in the reactive barrier between glass and the SiC of base material.Which avoid any chemical reaction between glass and SiC at the glazing temperature of glass, at the glazing temperature of glass, described reaction discharges gas and forms the source of the defect (bubble, hole) observed in the prior art;
The glass of likely glazing at lower than the temperature of 1100 DEG C composition is selected to avoid temperature CMC material being increased to the mechanical properties that may affect the fiber forming fibre-reinforced part; With
Selection second-order transition temperature makes likely to give the self-reparing capability of coating from described temperature lower than the glass composition of 750 DEG C.
Advantageously, tinting material is added comprise in the slurry of glass powder.Except the consideration of decorated type, depend on its character, add this tinting material and can give special advantage:
Even if when damaging minimum, be convenient to detect damage by means of only visual inspection, described damage may be derived from impact especially; With
Particularly distinguish character by infrared signature decay imparting.
According to a feature of described method, the liquid of cement thickener is selected from: sodium silicate solution; Phosphoric acid solution; With monophosphate aluminium (Al (H 2pO 4) 3) solution.
According to another feature of described method, the first coating of refractory cements is formed with the minimum thickness being not less than 60 microns (μm).
Advantageously, glass powder is less than the powder constituent of 40 μm by particle diameter.
In a special embodiment, glass powder with molar percentage represent composed as follows:
The SiO of 55% to 65% 2
The B of 10% to 25% 2o 3
The Al of 7% to 15% 2o 3
At least one alkalimetal oxide of 1% to 12%
At least one of 1% to 20% is selected from ZrO 2, TiO 2, V 2o 5, ZnO, CaO, MgO and BaO oxide compound.
Advantageously, the second coating forming enamel has the thickness being not less than 100 μm.
In yet another aspect, the invention provides a kind of parts, described parts are had the CMC base material that comprises SiC and are provided with the coating of the type that can be obtained by aforesaid method.
The feature of this parts is that described coating is by being formed as follows:
With the first coating of the surface contact of described base material, described first coating is made up of refractory cements, and described refractory cements is made up of silicon-dioxide and aluminum oxide and the hollow space of filling in the fluctuating on described surface thus reduce its irregularity substantially; With
Form the second coating of glass enamel, described second coating forms primarily of the oxide compound of silicon, boron, aluminium and at least one alkaline-earth metal, and described glass has the melt temperature lower than 1100 DEG C and the second-order transition temperature lower than 750 DEG C.
Advantageously, enamel also contains toner.
Advantageously, the first coating of refractory cements has the minimum thickness being not less than 60 μm.
Advantageously, the second coating forming enamel has the thickness being not less than 100 μm.
In a special embodiment, the glass of enamel with molar percentage represent composed as follows:
The SiO of 55% to 65% 2
The B of 10% to 25% 2o 3
The Al of 7% to 15% 2o 3
At least one alkalimetal oxide of 1% to 12%
At least one of 1% to 20% is selected from ZrO 2, TiO 2, V 2o 5, ZnO, CaO, MgO and BaO oxide compound.
Accompanying drawing explanation
By reading, with the following explanation that the mode of unrestricted instruction provides, the present invention may be better understood.With reference to accompanying drawing, wherein:
Fig. 1 shows the high-level schematic making the principle of coating according to the present invention on the CMC parts comprising SiC;
Fig. 2 shows the consecutive steps in an embodiment of method of the present invention; With
Fig. 3 to 5 is for showing the photo of the outward appearance of the coating obtained in the various embodiments of the present invention.
Embodiment
Fig. 1 is the high-level schematic sectional view of the base material 10 being provided with coating 20 on the surface 12.
Base material 10 is made up of the CMC comprising fibre-reinforced part, the matrix densification of described fibre-reinforced part by being formed by SiC at least partly.The fiber of reinforcement can be carbon fiber or ceramic fiber.Ceramic fiber can be made up of SiC or oxide compound (such as aluminum oxide).Matrix can be the C-SiC matrix of SiC matrix or mixing, or for comprising SiC phase and PyC phase, B 4the matrix be arranged in order that C phase or Si-B-C alternate.Exist for the manufacture of this known method with the CMC material of the matrix formed by SiC at least partly.In order to manufacture to the parts of shaped, make the fiber preform that shape corresponds to component shape, then by CVI or by liquid technology (namely by one or more circulation, described circulation comprises liquid composition dipping then solidification and the pyrolytic precursors with comprising ceramic precursor polymkeric substance), densification is carried out to performing member.Can with particular reference to such as Publication about Document: US5738908, US5079039, US5246736 and US5965266.
The fiber preform forming CMC reinforcement can use various Weaving method (particularly by pendency braided fiber cord body or by three-dimensional or multi-layer braided) to obtain.The existence of yarn causes the ripple 12a in the surface 12 of base material 10, and these ripples have the height h of hundreds of microns usually.In addition, base material has the superficial roughness caused due to the residual porosity of matrix, and no matter it obtains in which way, and this anchor has several microns, the value (in surface level change) of usual 5 μm to 10 μm.
Coating 20 comprises the first coating 22 of the refractory cements be deposited directly on the surface 12 of base material 10, and the second coating 24 of the glass of formation enamel, and the second coating 24 of described glass limits the outside surface of coating 20.In the embodiment shown, enamel 24 is deposited directly on the first layer 22, but also likely introduces middle layer for the object of the coupling coefficient of expansion.
The first layer 22 is by filling at least partly by the ripple 12a on surface 12 and the coarse recess that formed thus weakening the irregularity on the surface 12 of base material 10.The first layer 22 also has reactive barrier function thus avoids the chemical reaction between the glass and the SiC of base material 10 of enamel 24.If there is no the first layer 22, particularly there is this reaction by under the high temperature needed for the glass glazing of enamel 24, discharges gaseous species simultaneously, and described gaseous species may cause in enamel 24 to comprise bubble or run through enamel 24 and form hole.The first layer 22 completely covering substrates surface 12 and its minimum thickness is preferably not less than 60 μm, usually in the scope of 100 μm to 300 μm.
The function of enamel 24 is the smooth outer surface forming glossy appearance.Enamel 24 also contributes to weakening surface irregularity extraly, particularly anchor.The thickness of enamel is preferably greater than 100 μm, usually in the scope of 100 μm to 400 μm.Too small thickness may be not enough to effectively fill residual anchor, and excessive thickness may promote to form crack.
Coating 20 can obtain (Fig. 2) as follows.
Refractory cements thickener is used on the surface 12 that first step 200 is included in base material 10.Cement thickener is obtained by mixed powder and liquid.Powder is advantageously most of by silicon-dioxide SiO 2and aluminium oxide Al 2o 3make, the composition of powder is preferably as follows (representing with molar percentage);
The SiO of 75% to 90% 2
The Al of 10% to 25% 2o 3
Such as, liquid is the solution of water glass, wherein SiO 2/ NaO 2mol ratio preferably in the scope of 1 to 2.Other solution can be used, such as phosphoric acid solution or monophosphate aluminium (Al (H 2pO 4) 3) solution.
Cement thickener is by obtaining than mixed liquid medium and powder with the liquid/powder weight such as in 1 to 2 scope.
Likely add the additive of the organic forms with plasticising or super plasticising character thus cement thickener is more flowed, the sulfonated salts of such as trimeric cyanamide or naphthalene and formaldehyde condensation products.
Cement thickener by any known conventional means, such as, uses spatula, hairbrush or spray gun, uses on the surface 12.
Once cement solidifies (step 202) after a number of hours at ambient temperature in open air, heat-treat (step 204) thus curing cement.Such as, the little time up to a few hours is carried out in thermal treatment under 400 DEG C to the temperature within the scope of 600 DEG C.This generates substantially by SiO 2and Al 2o 3together with NaAlSiO 4the refractory cements that (when the liquid for cement thickener is the solution of sodium compound (such as water glass)) forms.
Select the amount of the cement thickener used thus ensure that refractory cements layer has required thickness after the heat treatment.
Step (206) is subsequently included on refractory cements layer uses slurry, and described slurry is made up of the glass powder in liquid suspension.Liquid is advantageously water, but likely uses other liquid, such as ethyl cellulose in Terpineol 350 10% solution.Glass powder is obtained by the glass of the composition selected by grinding thus prepares the enamel with required character, and described character is in particular:
Preferably lower than 750 DEG C, such as at 600 DEG C to the second-order transition temperature within the scope of 650 DEG C, second-order transition temperature is such temperature, can obtain the selfreparing of enamel higher than described temperature by forming the softening of the glass of enamel;
Preferably lower than the glazing temperature of 1100 DEG C, wherein glazing temperature is such temperature, glass powder needs to be increased to described temperature thus realizes enough low viscosity thus can sprawl with uniform thickness substantially, and the glazing temperature of 1100 DEG C or higher can affect the mechanical properties of the fiber of the fibre-reinforced part of CMC base material;
The preferably close thermal expansivity comprising the CMC base material of SiC, such as, 4 × 10 -6k -1to 5 × 10 -6k -1scope in; With
Good mechanical endurance, particularly good moisture resistance.
The composition of glass powder is the composition of the glass of the enamel obtained subsequently equally, such as, can be following (representing with molar percentage), be namely essentially the composition of aluminium borosilicate glass:
The SiO of 55% to 65% 2
The B of 10% to 25% 2o 3
The Al of 7% to 15% 2o 3
At least one alkalimetal oxide of 1% to 12%
At least one of 1% to 20% is selected from ZrO 2, TiO 2, V 2o 5, ZnO, CaO, MgO and BaO oxide compound.
Optionally add tinting material thus give the color needed for enamel.Can use various known tinting material, such as " cobalt blue ", " cobalt black " or cupric oxide CuO(are green).
Likely use commercially available glass or pass through the obtained glass with required ratio mixing and its composition of melting.
Abrading glass thus obtain particle diameter be less than 100 μm, be preferably less than the glass powder of 40 μm.
Slurry is used by any known conventional means, such as, use spatula to use.
In dry (step 208) with after removing liquid, progressively raised temperature thus make Glass Transition and sprawl (glazing), is maintained at the glazing temperature (step 210) of glass simultaneously by temperature.Glazing temperature is the function of the composition of glass, selects glass thus has and be preferably less than 1100 DEG C, such as at 1000 DEG C to the glazing temperature within the scope of 1100 DEG C.
Then preferably carry out lentamente cooling (step 212), thus freeze enamel with residual stress little as far as possible.The amount of the glass powder deposited can be selected thus terminate with the desired thickness of enamel.This generates the smooth-flat-surface with likely painted glossy appearance.For for the CMC parts in turbine engine, this coating provides good aerodynamic property, makes to be easy to by means of only visual inspection test example as being derived from the fault of impact simultaneously.In addition, can use painted thus give special character, the infrared signature particularly decayed.
The embodiment preparing coating of the present invention is described below.In all embodiments, base material is made up of SiC/SiC type CMC, comprises by the thread reinforcement of SiC silvalin together with multi-layer braided with the SIC matrix obtained by CVI.
embodiment 1
By mixing by SiO 2and Al 2o 3mixture (SiO 2/ Al 2o 3mol ratio equals about 1/8) powder formed and the liquid (SiO be made up of sodium silicate solution 2/ Na 2o mol ratio equals about 3/2) prepare refractory cements thickener.The weight ratio of liquid/powder is about 1.5.
Use spatula to be applied on the surface of base material by cement thickener, select its thickness thus obtain the final refractory cements layer that minimum thickness is about 100 μm.
The assembly comprising base material and cement thickener leaves standstill about 24 hours (h) at ambient temperature thus allows to the cement solidifies in open air.
Then at about 600 DEG C, heat-treat the time of about 2h in atmosphere.
By grinding have represent with molar percentage following composition (ignore impurity, glass if any) obtains glass powder:
The SiO of about 56% 2
The B of about 21% 2o 3
The Al of about 11% 2o 3
The CaO of about 5%
The BaO of about 5% and
The K of about 2% 2o
Carry out grinding thus obtain the particle diameter being less than about 40 μm.
Refractory cements coating uses spatula sprawl the slurry formed by the glass powder in distilled water suspensoid, select the amount of the glass powder used thus obtain the enamel that final thickness is about 300 μm.
After drying, progressively raised temperature is held in this temperature about 15 minutes (min) to about 1000 DEG C thus guarantees that uniform glass is sprawled substantially.
In atmosphere after Slow cooling, obtain the coating with level and smooth, gloss and unrippled outside surface.
embodiment 2
Step as embodiment 1, but glass powder have represent with molar percentage following composition (ignore impurity, if any):
The SiO of about 62% 2
The B of about 12% 2o 3
The Al of about 4% 2o 3
The ZnO of about 6%
The CaO of about 7%
The NaKO of about 5%
The ZrO of about 4% 2
In addition, in order to thermal treatment thus be refractory cements layer glazing enamel, the base material with refractory cements and glass powder directly to be inserted in the stove at 1000 DEG C and be maintained at this temperature and be about 15min, then with about-2 Kelvins/minute (K.min -1) control ground Slow cooling.
Fig. 3 shows the surface of the refractory cements layer before using enamel, and Fig. 4 shows the surface of enamel.Can see, still visible surface ripple on the surface of refractory cements layer, but external waviness almost disappears after using enamel.Compared to the value of 355 μm that record on initial substrate, scanning electron microscopic observation is used to show the average ripple magnitude of about 16 μm.
By the chemical durability of Soxhelt method tested glass, described Soxhelt method application ISO16797:2004 standard is by the leaching of the simulate glass in the closed circuit of the water at use 100 DEG C of temperature.After 800h, the mass loss relative value recorded is only 0.8%.
embodiment 3
Step as embodiment 2, but relative to the slurry be made up of glass powder and water weight with 5 % by weight ratio cobalt blue is added in slurry.
Obtain the blue coating with the smooth outer surface of enamel outward appearance.
embodiment 4
Step is as embodiment 3, but cobalt blue cobalt black replaces.
Fig. 5 shows the black coating with the smooth outer surface of enamel outward appearance of acquisition.

Claims (12)

1. on the base material of ceramic matrix composites, form a method with the coating of the smooth outer surface of enamel outward appearance, the base material of described ceramic matrix composites comprises silicon carbide, and described method comprises:
At the deposited on silicon refractory cements thickener of described base material, described thickener is by being formed with the powder of liquid mixing primarily of silicon-dioxide and aluminum oxide composition, and described cement thickener fills the hollow space in the fluctuating on described surface thus reduce its irregularity and cover the whole surface of described base material;
Heat-treat after theing cement solidifies thus solidify described cement, thus obtaining the first coating of refractory cements;
Deposited furnish in described first coating, described slurry is formed by the glass powder in liquid suspension, and described glass powder is formed primarily of the powder of silicon-dioxide, boron oxide, aluminum oxide and at least one alkalimetal oxide; With
Carry out the thermal treatment for glazing by softening and sprawling described glass thus obtain the second coating, described second coating formation covers the enamel of described first coating;
Select the composition of described glass powder thus formed glazing temperature lower than 1100 DEG C and second-order transition temperature lower than the glass of 750 DEG C.
2. method according to claim 1, wherein adds tinting material in described slurry.
3., according to method according to claim 1 or claim 2, the liquid of wherein said cement thickener is selected from: sodium silicate solution; Phosphoric acid solution; With monophosphate aluminium (Al (H 2pO 4) 3) solution.
4. method according to claim 1, wherein the first coating of refractory cements is formed with the minimum thickness being not less than 60 μm.
5. method according to claim 1, wherein said glass powder is less than the powder constituent of 40 μm by particle diameter.
6. method according to claim 1, wherein said glass powder with molar percentage represent composed as follows:
The SiO of 55% to 65% 2
The B of 10% to 25% 2o 3
The Al of 7% to 15% 2o 3
At least one alkalimetal oxide of 1% to 12%
At least one of 1% to 20% is selected from ZrO 2, TiO 2, V 2o 5, ZnO, CaO, MgO and BaO oxide compound.
7. method according to claim 1, the second coating wherein forming enamel has the thickness being not less than 100 μm.
8. comprise parts for the base material of ceramic matrix composites, the base material of described ceramic matrix composites comprises silicon carbide and is provided with the coating of the smooth outer surface with enamel outward appearance from the teeth outwards, and wherein said coating is by being formed as follows:
With the first coating of the surface contact of described base material, described first coating is made up of refractory cements, and described refractory cements is made up of silicon-dioxide and aluminum oxide and the hollow space of filling in the fluctuating on described surface thus reduce its irregularity substantially; With
Form the second coating of glass enamel, described second coating forms primarily of the oxide compound of silicon, boron, aluminium and at least one alkaline-earth metal, and described glass has the melt temperature lower than 1100 DEG C and the second-order transition temperature lower than 750 DEG C.
9. parts according to claim 8, wherein said enamel also contains toner.
10. according to Claim 8 or parts according to claim 9, wherein the first coating of refractory cements has the minimum thickness being not less than 60 μm.
11. parts according to claim 8, the second coating wherein forming enamel has the thickness being not less than 100 μm.
12. parts according to claim 8, it is characterized in that the glass of described enamel with molar percentage represent composed as follows:
The SiO of 55% to 65% 2
The B of 10% to 25% 2o 3
The Al of 7% to 15% 2o 3
At least one alkalimetal oxide of 1% to 12%
At least one of 1% to 20% is selected from ZrO 2, TiO 2, V 2o 5, ZnO, CaO, MgO and BaO oxide compound.
CN201280043276.7A 2011-09-06 2012-08-31 The base material be made up of the ceramic matrix composites comprising SiC is formed the method for level and smooth enamel coating, and the parts be made up of the ceramic matrix composites being provided with described coating Expired - Fee Related CN103827056B (en)

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FR1157890A FR2979629B1 (en) 2011-09-06 2011-09-06 METHOD OF FORMING ON A CMC SUBSTRATE CONTAINING SIC OF A SMOOTH COATING OF ICE ASPECT AND CMC PART PROVIDED WITH SUCH COATING
FR1157890 2011-09-06
PCT/FR2012/051964 WO2013034838A1 (en) 2011-09-06 2012-08-31 Method for forming a smooth glaze-like coating on a substrate made of a ceramic matrix composite material containing sic, and part made of a ceramic matrix composite material provided with such a coating

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JP6300398B2 (en) * 2013-09-30 2018-03-28 三菱重工業株式会社 Method for manufacturing fluid machine member
CN104892031B (en) * 2014-12-09 2017-08-25 大汉国际控股有限公司 A kind of super-smooth glaze and preparation method thereof
EP3159325B1 (en) 2015-10-22 2020-07-08 Rolls-Royce High Temperature Composites Inc Reducing impurities in ceramic matrix composites
CN111058018A (en) * 2019-12-26 2020-04-24 兰州空间技术物理研究所 Preparation method of oxidation-resistant coating on surface of TD3 alloy
US20220041519A1 (en) * 2020-08-05 2022-02-10 General Electric Company Method for repairing composite components using filler material
CN112341000B (en) * 2020-11-27 2023-01-03 西北工业大学 Carbon/carbon composite material SiC coating repairing modified glass material based on laser cladding method and preparation and use methods
CN113800950B (en) * 2021-08-27 2023-04-07 咸阳盈和电子材料有限公司 Glass coating for surface of silicon carbide rod and preparation method thereof
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1062961A (en) * 1990-12-26 1992-07-22 华兴航空机轮公司 Carbon/carbon compound material brake disc high-temperature oxidation resistant coating
CN1718560A (en) * 2005-06-29 2006-01-11 中国人民解放军国防科学技术大学 Carbon-fiber reinforced silicon carbide composite material antioxidation coating layer and its preparation method

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58176187A (en) * 1982-03-29 1983-10-15 イビデン株式会社 Silicon carbide substrate and manufacture
FR2643898B1 (en) 1989-03-02 1993-05-07 Europ Propulsion PROCESS FOR THE MANUFACTURE OF A COMPOSITE MATERIAL WITH A CERAMIC MATRIX WITH IMPROVED TENACITY
FR2668477B1 (en) 1990-10-26 1993-10-22 Propulsion Ste Europeenne REFRACTORY COMPOSITE MATERIAL PROTECTED AGAINST CORROSION, AND METHOD FOR THE PRODUCTION THEREOF.
FR2714076B1 (en) 1993-12-16 1996-03-15 Europ Propulsion Method for densifying porous substrates by chemical vapor infiltration of silicon carbide.
US6479104B1 (en) * 1994-04-29 2002-11-12 Mcdonnell Douglas Corporation Cementitious ceramic surface having controllable reflectance and texture
FR2732338B1 (en) 1995-03-28 1997-06-13 Europ Propulsion COMPOSITE MATERIAL PROTECTED AGAINST OXIDATION BY SELF-HEALING MATRIX AND MANUFACTURING METHOD THEREOF
FR2838071B1 (en) * 2002-04-09 2004-07-09 Snecma Propulsion Solide PROTECTION AGAINST OXIDATION OF COMPOSITE MATERIALS
FR2944010B1 (en) * 2009-04-02 2012-07-06 Snecma Propulsion Solide METHOD FOR SMOOTHING THE SURFACE OF A PIECE OF CMC MATERIAL

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1062961A (en) * 1990-12-26 1992-07-22 华兴航空机轮公司 Carbon/carbon compound material brake disc high-temperature oxidation resistant coating
CN1718560A (en) * 2005-06-29 2006-01-11 中国人民解放军国防科学技术大学 Carbon-fiber reinforced silicon carbide composite material antioxidation coating layer and its preparation method

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